Width of Homopolymer Interfaces in the Presence of Symmetric Diblock Copolymers

Abstract

The interface between polystyrene and poly(methyl methacrylate) homopolymers was investigated as a function of the concentration of added symmetric diblock copolymer of PS and PMMA, denoted P(S-b-MMA), using neutron reflectivity. It was found that as the number of P(S-b-MMA) chains added to the interface between PS and PMMA was increased, the width of the gradient between the PS and PMMA segments broadened. In particular, the width of the interface between PS and PMMA homopolymers is 50 Å and, with the addition of P(S-b-MMA), increases to ~85 Å. At an amount corresponding to approximately half the thickness of the lamellar microdomain periodicity in the bulk, the interface becomes saturated with the copolymer. Further addition of copolymer chains to the interface results in a marked increase in the off-specular scattering, which is associated with either an ordering of the copolymer chains at the interface or an increase in the curvature of the interface. Studies were also performed on mixtures of homopolymers and copolymers. Here, the interface between the lamellar microdomains of the P(S-b-MMA) is found to increase from 50 Å for the pure copolymer to 75 Å as PS and PMMA homopolymer is added to the copolymer. The broadening of the interface seen in both sets of experiments is due to a significant penetration of the homopolymer into the interfacial region. These results are consistent with the reduction in the interfacial tension between the homopolymers with the addition of the diblock copolymer. © 1991, American Chemical Society. All rights reserved.